Inks are illustrated in U.S. Pat. No. 6,187,082; U.S. Ser. No. 09/281,540, now abandoned; U.S. Pat. Nos. 6,096,124, 6,071,333, 6,086,661, 6,096,125, 6,106,601; and 5,931,995, 5,902,390, 5,876,492, 5,922,117, and 6,066,200; the disclosures of each being totally incorporated herein by reference.
The appropriate components and processes of the copending applications, including the above parent application, may be selected for the present invention in embodiments thereof.
The present invention is directed to ink compositions and, more specifically, the present invention relates to inks with, for example, a melting point of between about 60xc2x0 C. and about 150xc2x0 C., and preferably between about 70xc2x0 C. to about 90xc2x0 C., especially useful for acoustic ink printing, processes and apparatuses, reference, for example, U.S. Pat. Nos. 5,121,141, 5,111,220, and 5,371,531, the disclosures of which are totally incorporated herein by reference, including especially acoustic ink processes as illustrated in the above copending applications, such as an acoustic ink printer for printing images on a record medium. The inks of the present invention in embodiments thereof are comprised of (1) a phase change ink, that is, for example, an ink that changes from a liquid state to solid state in a suitable period of time, for example, from about 1 to about 100 milliseconds and preferably in less than about 10, such as from about 2 to about 7 milliseconds, and which inks contain a nonaqueous phase-change color spreading compound, or an additive, such as a long chain carbamate or an oxazoline compound that, for example, can fill the pores of a substrate, such as paper, with a melting point of lower than about 120xc2x0 C. and preferably between about 60 to about 100xc2x0 C., and with a low acoustic loss value of below about 100 dB/mm; (2) a nonaqueous crease improving carbamate, thiourea, or mixtures thereof with, for example, a boiling point of higher than about 150xc2x0 C. (Centigrade) and more specifically with a boiling point from about 150 to about 225xc2x0 C., and a melting point of between about 25 to about 100xc2x0 C., and preferably between about 60 to about 100xc2x0 C., with low acoustic loss, which primarily enables a reduction or minimization of energy consumption, and which acoustic loss is below, or about equal to 60 dB/mm; (3) a gloss improving alcohol compound; (4) a lightfastness component, such as a lightfastness UV absorber; (5) a lightfastness antioxidant; (6) a colorant such as a dye, a pigment or mixtures thereof; (7) a plasticizer, such as o,p-toluene sulfonamide (Uniplex 171), p-toluene sulfonamide (Uniplex 173), dicyclohexyl phthalate (Uniplex 250), dimethylisophthalate (Uniplex 270), pentaerythriol tetrabenzoate (Uniplex 552), or mixtures thereof; and (8) an optional clarifying agent such as Mn1Ri2 1500/2000 series polyamides, Mn1-Ri2 7000/8000 series maleic rosin resins, Mn1-Ri2 4000/9000 series modified phenolic rosin resins, or mixtures thereof.
More specifically, the present invention is directed to phase-change acoustic ink compositions comprised of (1) a nonaqueous long chain carbamate compound with, for example, a melting point of lower than about 120xc2x0 C. and preferably between about 60xc2x0 C. and about 100xc2x0 C., and with a low acoustic loss, and which acoustic loss is, for example, below about or equal to about 100 dB/mm, and preferably from about 25 to about 80 dB/mm; (2) blends of long chain carbamates dB/mm; (3) a crease improving plasticizer; (4) a clarifier; (5) a gloss improving alcohol compound with a boiling point of, for example, higher than about 150xc2x0 C. and lower than about 350xc2x0 C., preferably between about 170xc2x0 C. to about 220xc2x0 C., and a melting point of, for example, between about 25xc2x0 C. to about 90xc2x0 C. and with a low acoustic loss, and which acoustic loss is, for example, below about 60 dB/mm, and preferably in the range of between about 5 to about 40 dB/mm; (6) a lightfastness compound, such as a UV absorber; (7) an antioxidant; (8) a colorant, and wherein there can be generated with such inks excellent developed images on plain and coated papers with acceptable image permanence, excellent projection efficiency on transparencies without a post fusing step, and excellent crease resistance, and wherein the inks possess acceptable, and in embodiments superior lightfast, for example about 90 to about 100 percent and superior waterfast between, for example, about 95 to about 100 percent.
Blending long chain carbamates, especially two such carbamates, with different side chain lengths, for example, one with 16 carbon atoms and the other with 18 carbon atoms in the side chain, can reduce the spherulite size and improves crease, projection efficiency and haze. With blends, the amount of plasticizers and clarifiers in the compositions can be reduced to suitable amounts or one of them eliminated.
The blends can contain sufficient amounts of each carbamate and wherein the total thereof is about 100 percent, for example from about 1 to about 99 percent of one carbamate and from about 99 to about 1 percent of a second carbamate. Blends can include, for example, from about 1 to about 5 carbamates.
Moreover, in embodiments of the present invention there is enabled the elimination, or minimization of undesirable paper curl since water need not be present, or minimum amounts less than, for example, about 1 percent of water may be selected in embodiments, and in embodiments it is preferred that there be an absence of water. When water is not present in the inks, a dryer can be avoided thereby minimizing the cost of the acoustic ink jet apparatus and process.
In acoustic ink printing, the printhead produces approximately 2.2 picoliter droplets by an acoustic energy process. The ink under these conditions should display a melt viscosity of about 5 centipoise or less at the jetting temperature. Furthermore, once the ink is jetted onto the paper, the ink image should be of excellent crease property, and should be nonsmearing waterfast, of excellent transparency and excellent fix qualities. In selecting an ink for such applications, it is desirable that the vehicle display a low melt viscosity, such as from about 1 centipoise to about 25 centipoise in the acoustic head, while also displaying solid like properties after being jetted onto paper. Since the acoustic head can tolerate a temperature up to about 180xc2x0 C., and preferably up to a temperature of from about 140xc2x0 C. to about 160xc2x0 C., the vehicle for the ink should preferably display liquid like properties such as a viscosity of 1 to about 10 centipoise at a temperature of from about 75xc2x0 C. to about 165xc2x0 C., and solidify or harden after jetting onto paper such that the ink displays a hardness value of from about 0.1 to about 0.5 millimeter utilizing a penetrometer according to the ASTM penetration method D1321.
Ink jet printing processes that employ inks that are solid at room temperature and liquid at elevated temperatures are known. For example, U.S. Pat. No. 4,490,731, the disclosure of which is totally incorporated herein by reference, discloses an apparatus for dispensing certain solid inks for printing on a substrate such as paper. The ink dye vehicle is chosen to have a melting point above room temperature so that the ink, which is melted in the apparatus, will not be subject to evaporation or spillage during periods of nonprinting. The vehicle selected possesses a low critical temperature to permit the use of the solid ink in a thermal ink jet printer. In thermal ink jet printing processes employing these phase-change inks, the solid ink is melted by a heater in the printing apparatus and utilized as a liquid in a manner similar to that of conventional thermal ink jet printing. Upon contact with the printing substrate, the molten ink solidifies rapidly, enabling the dye to remain on the surface instead of being carried into the paper by capillary action, thereby attempting to enable higher print density than is generally obtained with liquid inks. Phase-change ink jets are somewhat similar to thermal ink jets; however, a phase-change ink usually contains no solvent. Thus, rather than being liquid at room temperature, a phase-change ink is typically a solid with a wax-like consistency. These inks usually are heated, for example, to approximately 100xc2x0 C. before the ink melts and converts to a liquid. With phase-change inks, a plurality of ink jet nozzles is provided in a printhead, and a piezoelectric vibrating element is located in each ink channel upstream from a nozzle so that the piezoelectric oscillations propel ink through the nozzle. After the phase-change ink is applied to the substrate, freezing on the substrate resolidifies the ink.
Each of these types of known ink jets, however, has a number of advantages and disadvantages. One advantage of thermal ink jets is their compact design for the integrated electronics section of the printhead. Thermal ink jets are disadvantageous in that the thermal ink has a tendency to soak into a plain paper medium. This blurs the print or thins out the print locally thereby adversely affecting print quality. Problems have been encountered with thermal ink jets in attempting to rid the ink of moisture fast enough so that the ink does not soak into a plain paper medium. This is particularly true when printing with color. Therefore, usually when printing with thermal ink coated papers are used, which papers are more costly than plain paper.
One advantage of phase-change ink is its ability to print on plain paper since the phase-change ink quickly solidifies as it cools and, since it is primarily waxy in nature, it does not normally soak into a paper medium. However, phase-change ink jet systems can be cumbersome in structure and in design, that is, the associated integrated electronics of a thermal ink jet head are considerably more compact than those of a phase-change ink jet head.
U.S. Pat. No. 4,751,528, the disclosure of which is totally incorporated herein by reference, discloses a phase-change ink jet system which includes a temperature-controlled platen provided with a heater and a thermoelectric cooler electrically connected to a heat pump and a temperature control unit for controlling the operation of the heater and the heat pump to maintain the platen temperature at a desired level. The apparatus also includes a second thermoelectric cooler to solidify phase-change ink in a selected zone more rapidly to avoid offset by a pinch roll coming in contact with the surface of the substrate to which phase-change ink has been applied. An airtight enclosure surrounding the platen is connected to a vacuum pump and has slits adjacent to the platen to hold the substrate in thermal contact with the platen.
Further, U.S. Pat. No. 4,791,439, the disclosure of which is totally incorporated by reference, discloses an apparatus for use with phase-change inks with an integrally connected ink jet head and reservoir system, the reservoir system including a highly efficient heat conducting plate inserted within an essentially nonheat conducting reservoir housing.
Ink compositions for ink jet printing are known are illustrated, for example, in U.S. Pat. No. 4,840,674, the disclosure of which is totally incorporated herein by reference, and which patent discloses an ink composition which comprises a major amount of water, an organic solvent selected from the group consisting of tetramethylene sulfone, 1,1,3,3-tetramethyl urea, 3-methyl sulfolane, and 1,3-dimethyl-2-imidazolidone, which solvent has permanently dissolved therein spirit soluble dyes.
U.S. Pat. Nos. 5,006,170 and 5,122,187, the disclosures of each of which are totally incorporated herein by reference, disclose ink compositions suitable for ink jet printing which comprise a colorant, a binder, and a propellant such as hydrazine, cyclic amines, ureas, carboxylic acids, sulfonic acids, aldehydes, ketones, hydrocarbons, esters, phenols, amides, imides, halocarbons, and the like.
U.S. Pat. No. 5,041,161, the disclosure of which is totally incorporated herein by reference, discloses an ink jet ink, which is phase-change ink at room temperature. The inks comprise vehicles, such as acids, aldehydes and mixtures thereof, and which inks can be impulse jetted at an elevated temperature in the range of about 45xc2x0 C. to about 110xc2x0 C.
U.S. Pat. Nos. 4,853,036 and 5,124,718 disclose an ink for ink jet recording and which ink comprises a liquid composition essentially comprising a coloring matter, a volatile solvent with a vapor pressure of 1 millimeter Hg or more at 25xc2x0 C., and a compound being solid at room temperature and having a molecular weight of 300 or more.
U.S. Pat. No. 5,667,568 discloses an ink composition comprised of a colorant and a bisamide with a viscosity of from about 1 centipoise to about 20 centipoise at a temperature of from about 125xc2x0 C. to about 185xc2x0 C.
U.S. Pat. No. 5,698,017 discloses an ink composition comprised of a colorant and a vehicle component, and which vehicle component is comprised of the condensation product of an organic acid and an amino alcohol.
U.S. Pat. No. 5,693,128 discloses an ink composition comprised of a colorant and a reversible crosslinked component vehicle obtained from the reaction product of an anhydride and an organoamine, and which ink possesses a viscosity of from about 1 centipoise to about 25 centipoise at a temperature of from about 125xc2x0 C. to about 185xc2x0 C.
U.S. Pat. No. 5,700,316 discloses an ink composition comprised of a colorant and a vehicle of a poly(alkylene oxide)-alkylate, a poly(alkylene oxide)-dialkylate, a polyoxa-alkanoate ester, or a polyoxa-alkanedioate diester, and which ink possesses a viscosity of from about 1 centipoise to about 15 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C.
While the known ink compositions and processes may be suitable for their intended purposes, a need remains for acoustic phase-change ink compositions suitable for ink jet printing. In addition, there is a need for phase-change ink compositions, which are compatible with a wide variety of plain papers and yield photographic quality images on plain and coated papers. Further, there is a need for phase-change ink compositions, which generate high quality, lightfast, and waterfast images on plain papers. There is also a need for phase-change ink jet ink compositions which generate high quality, fast-drying images on a wide variety of plain papers at low cost with high quality text and high quality graphics, and wherein the colorant, such as the dye, is retained on the paper surface while the ink vehicle can continue to spread within the paper structure. Further, there is a need for phase-change ink jet ink compositions, which exhibit minimal feathering. Additionally, there is a need for phase-change ink jet ink compositions, which exhibit minimal intercolor bleed. There is also a need for phase-change ink jet ink compositions, which exhibit excellent image permanence. Further, there is a need for phase-change ink jet ink compositions, which are suitable for use in acoustic ink jet printing processes. Additionally, there is a need for phase-change hot ink compositions suitable for ink jet printing processes wherein the substrate is heated prior to printing and is cooled to ambient temperature subsequent to printing (heat and delay printing processes). There is also a need for ink compositions suitable for ink jet printing wherein high optical densities can be achieved with relatively low dye concentrations. A need also remains for ink compositions suitable for ink jet printing wherein curling of the substrate, such as paper, subsequent to printing is minimized, or avoided. Another need resides in inks with a spherulite (spherical ink crystals) size during solidification that can be reduced from, for example, the conventional more than about 10 micrometers to about 2 to about 4 micrometers, and in embodiments to about 1 to about 3 micrometers, utilizing plasticizers, clarifiers, and/or blends of long chain carbamates or by crystallinity inhibitor diluents derived from low melting alcohols to thereby, for example, improve projection efficiency and crease resistance. There is also a need for low viscosity inks, thereby permitting, for example, reduced power consumption by about 35 percent thereby increased printing speed from, for example, about 25 pages per minute to about 40 pages per minute, and which inks can enable improved jettability resulting in excellent ink directionality and consequently lower edge raggedness of the prints such as a value of about 5 microns and preferably lower than about 3 microns. The edge raggedness is the deviation of the average width of a line measured from the middle of the line to the edge of the line (also known as mid-frequency line-edge noise (MFLN)) and can be measured with an optical microscope. Moreover, there is a need for inks that generate images that are durable (crease less than about 60) and can withstand the pressures of paper folding such that there is substantially no loss, or no loss of information, wherein crease is measured on images printed with the inks of the present invention in the same known manner as used in the evaluation of xerographic images. The average width of the creased image due to pressure can be obtained on colored and black solid area images printed on paper by (a) folding inwards the printed area of the image; (b) passing on the folded image a standard TEFLON(copyright) coated copper roll 2 inches in width, 3 inches in outer diameter, 2.25 inches in inner diameter and weighing 860 grams; (c) unfolding the paper and wiping the loose toner from the creased imaged surface with a cotton swab; and (d) measuring the average width of the ink free creased area with an image analyzer.
These and other needs can be achievable with the inks of the present invention in embodiments thereof.
Aspects of the present invention relate to an ink composition comprised of (1) an oxazoline compound with an optional point of from about 60xc2x0 C. to about 120xc2x0 C. and an optional acoustic-loss value of from about 25 to about 80 dB/mm; (2) a carbamate; (3) an alcohol compound; (4) a lightfastness component; (5) a lightfastness antioxidant; and (6) a colorant, and wherein the carbamate is a long chain carbamate; an ink composition comprised of (1) a long chain simple carbamate compound with an optional melting point of from about 60xc2x0 C. to about 120xc2x0 C. and an optional acoustic-loss value of from about 25 to about 80 dB/mm; (2) a plasticizer compound with an optional melting point of from about 25xc2x0 C. to about 100xc2x0 C.; (3) an optional clarifier compound; (4) a lightfastness component; (5) a lightfastness antioxidant; and (6) a colorant; an ink composition wherein a mixture of the long chain carbamates is selected, which mixture optionally contains from about 5 weight percent to about 95 weight percent of each carbamate, and wherein the total thereof is about 100 percent; an ink composition wherein (1) the long chain carbamate is a solid compound possessing an acoustic-loss value of from about 25 to about 80 dB/mm; and (2) the plasticizer possesses an acoustic-loss value of from about 5 to about 40 dB/mm; an ink composition wherein the carbamate compound is present in an amount of from about 15 to about 90 percent by weight, the plasticizer is present in an amount of from about 35 to about 4 percent by weight, the clarifier is present in an amount of from about 25 to about 3 percent by weight, the lightfastness component is present in an amount of from about 5 to about 1 percent by weight, the antioxidant is present in an amount of from about 5 to about 1 percent by weight, and the colorant is present in an amount of from about 15 to about 1 percent by weight, and wherein the total amount of the ink components is about 100 percent; an ink composition wherein the long chain carbamate compound is selected from the group consisting of side chain carbamates of a CnHs(2n+1), where n is from about 6 to about 18; and s represents a side chain carbamate, an ink composition wherein the carbamate is stearylcarbamoyl octanoate; an ink composition wherein the plasticizer is o,p-toluene sulfonamide (UNILEX 171(trademark)), p-toluene sulfonamide (UNILEX 173(trademark)), dicyclohexyl phthalate (UNIPLEX 250(trademark)), dimethylisophthalate (UNIPLEX 270(trademark)), pentaerythritol tetrabenzoate) (UNIPLEX 552(trademark)), or mixtures thereof, each with an optional melting point of between about 25xc2x0 C. to about 100xc2x0 C., each with an optional low acoustic loss, which primarily enables a reduction or minimization of energy consumption, and which acoustic loss is optionally below, or about equal to 60 dB/mm; an ink composition wherein the clarifying agent is a UNI-REZ 1500/2000(trademark) series polyamide, UNI-REZ 7000/8000(trademark) series maleic rosin resins, UNI-REZ 4000/9000(trademark) series modified phenolic rosin resins, or mixtures thereof; an ink composition wherein the clarifying agent is present in an amount of from about 1 to about 20 weight percent; an ink composition wherein the lightfastness component is selected from the group consisting of (1) 1,1-(1,2-ethane diyl) bis(3,3,5,5-tetramethyl piperazinone); (2) 6-ethoxy-1,2-dihydro-2,2,4-trimethyl quinoline; (3) 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate; (4) 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)succinimide; and (5) 1,2,2,6,6-pentamethyl-4-piperidinyl/xcex2,xcex2,xcex2xe2x80x2,xcex2xe2x80x2,-tetra methyl-3,9-(2,4,8,10-tetraoxospiro(5,5)undecane)diethyl]-1,2,3,4-butane tetracarboxylate; an ink composition wherein the lightfastness antioxidant compound is selected from the group consisting of (1) antimony dialkyl phosphorodithioate; (2) molybdenum oxysulfide dithio carbamate; (3) nickel-bis(o-ethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate; and (4) tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate; a printing process which comprises incorporating into an acoustic ink jet printer the ink of the present invention, and causing droplets of the ink to be ejected in imagewise pattern onto a substrate; a process wherein there are generated developed images with crease values of from about 8 to about 15, haze values of from about 10 to about 18, gloss values of from about 85 to about 90, and which ink possesses an acoustic-loss value of from about 10 to about 80 dB/mm; and which ink possesses a viscosity of from about 1 centipoise to about 25 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C.; a process which comprises providing an acoustic ink printer having a pool of the ink of the present invention and causing droplets of the ink to be ejected in imagewise pattern onto a substrate; a process wherein there are generated images with crease values of from about 8 to about 14, haze values of from about 10 to about 18, gloss values of from about 80 to about 95; and which ink possesses an acoustic-loss value of from about 10 to about 80 dB/mm; and which ink possesses a viscosity of from about 1 centipoise to about 25 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C.; an ink composition wherein the colorant is selected in an amount of from about 0.5 to about 20 percent by weight; an ink composition wherein the colorant is a pigment, or a dye; an ink composition with a viscosity of from about 1 centipoise to about 10 centipoise at from about 60xc2x0 C. to about 120xc2x0 C., and which ink generates developed images with crease values of from about 8 to about 15, haze values of from about 10 to about 18, and gloss values of from about 85 to about 90; a composition comprised of (1) a carbamate; (2) a plasticizer; (3) a clarifier compound; (4) a lightfastness compound; (5) an antioxidant, and (6) a colorant; and wherein the carbamate is a straight chain carbamate; a composition wherein the carbamate is a long chain carbamate with a melting point of from about 60xc2x0 C. to about 120xc2x0 C. and an acoustic-loss value of from about 25 to about 80 dB/mm; an ink composition which possesses an acoustic-loss value of from about 10 to about 80 dB/mm, and which ink possesses a viscosity of from about 1 centipoise to about 25 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C., and which ink is substantially free of water; a composition wherein the carbamate is stearylcarbamoyl octanoate, stearylcarbamoyl dodecanoate, stearylcarbamoyl hexadecanoate, or stearylcarbamoyl octadecanoate optionally present in an amount of from about 40 to about 90 percent; an ink composition wherein the plasticizer is selected in an amount of about 5 to about 40 percent, and wherein the carbamate is present in an amount of from about 60 weight percent to about 80 weight percent; an ink composition wherein the long chain carbamate is stearylcarbamoyl octanoate, stearylcarbamoyl dodecanoate, stearylcarbamoyl hexadecanoate, or stearylcarbamoyl octadecanoate; inks comprised of (1) a solid oxazoline compound with a melting point of, for example, (about throughout, especially for ranges and component listings) from about 60xc2x0 C. to about 120xc2x0 C. and an acoustic-loss value of from about 25 to about 80 dB/mm; (2) a carbamate compound with a melting point of from about 25xc2x0 C. to about 100xc2x0 C.; (3) an alcohol compound; (4) a lightfastness component; (5) a lightfastness antioxidant; and (6) a colorant; an ink composition wherein (1) the solid oxazoline compound possesses an acoustic-loss value of from about 25 to about 80 dB/mm; and (2) the carbamate possesses an acoustic-loss value of from about 5 to about 40 dB/mm; an ink composition wherein the oxazoline compound is present in an amount of from about 15 to about 90 percent by weight, the carbamate is present in an amount of from about 35 to about 4 percent by weight, the alcohol is present in an amount of from about 25 to about 3 percent by weight, the lightfastness component is present in an amount of from about 5 to about 1 percent by weight, the antioxidant is present in an amount of from about 5 to about 1 percent by weight, and the colorant is present in an amount of from about 15 to about 1 percent by weight, and wherein the total amount of the ink components is about 100 percent or 100 parts; an ink composition wherein the oxazoline compound is selected from the group consisting of (1) 5-(hydroxymethyl)-5xe2x80x2(methoxy stearate)oxazoline; (2) 2-stearyl-5-(hydroxymethyl)-5xe2x80x2(methoxy stearate)oxazoline; (3) mixtures thereof, and the like; an ink composition wherein the carbamate compound is selected from the group consisting of (1) butyl carbamate; (2) tert-butyl carbamate; (3) tert-butyl N-(3-aminopropyl) carbamate; (4) tert-butyl N-(3-hydroxypropyl) carbamate; (5) tert-butyl-N-benzyloxy)-carbamate; (6) tert-butyl-N-hydroxycarbamate; (7) tert-butyl-N-allylcarbamate; (8) tert-butyl-N-(tert-butoxycarbonyloxy) carbamate; (9) tert-butyl-N-[2-hydroxy-2-(hydroxyphenyl)-1-methylethyl]carbamate; (10) tert-butyl-(2,4-dinitrophenoxy) carbamate; (11) benzyl carbamate; (12) benzyl N-hydroxycarbamate; (13) benzyl N-(2-hydroxyethyl)carbamate; (14) benzyl-N,N-dimethyldithiocarbamate; (15) ethyl N-methyl-N-phenylcarbamate; (16) ethyldiphenylcarbamate; (17) cyanomethyl-N,N-dimethyl-dimethyldithio carbamate; (18) 4,4xe2x80x2-methylene-bis(dibutyldithio carbamate); (19) potassium N-hydroxymethyl-N-methyl-dithiocarbamate; (20) sodium dimethyl dithiocarbamate; (21) disodium ethylenebis-dithio carbamate; (22) diethylammonium diethyldithio carbamate; (23) benzyl(S)-(xe2x88x92)-tetrahydro-5-oxo-3-furanyl carbamate; (24) diethyldithiocarbamic acid, ammonium salt; (25) diethyldithiocarbamic acid, diethyl ammonium salt; (26) diethyldithiocarbamic acid, sodium salt, and (27) 4-bromo-3,5-dimethylphenyl N-methylcarbamate benzyl N-(2-hydroxyethyl)carbamate; an ink composition wherein the alcohol is (1) a cycloalkyl alcohol wherein alkyl contains from about 6 to about 12 carbon atoms; (2) 4-tert-butyl cyclohexanol; (3) 3-aminomethyl-3,5,5-trimethyl cyclohexanol; (4) 2,2,6,6-tetrachloro cyclohexanol; (5) cycloalkane methanol where the number of carbon atoms in the alkane chain vary from about 5 to about 12; (6) dicyclohexylmethanol; (7) 3-cyclohexyl-1-propanol; (8) 2-amino-3-cyclohexyl-1-propanol; (9) (S)-2-(tert-butoxy carbonyl amino)-3-cyclohexyl-1-propanol; (10) cycloalkane diol where the number of carbons in the alkane chain vary from about 5 to about 8; (11) cis-3,5-cyclohexadiene-1,2-diol; (12) xcfx81-menthane-3,8-diol; (13) cyclohexane dimethanol; (14) 3-cyclohexene-1,1-dimethanol; (15) 1,3-dioxane-5,5-dimethanol; or (16) piperidine methanol cycloalkyl alcohol; an ink composition wherein the alcohol is a linear alcohol selected from the group consisting of (1) alkyl alcohols where the number of carbons in the alkyl chain vary from about 6 to about 22; and (2) alkane diols where the number of carbons in the alkane chain vary from about 5 to about 14; an ink composition wherein the alcohol is a linear alcohol selected from the group consisting of (a) 5-amino-1-pentanol; (b) nitromethane trispropanol; (c) 6-amino-1-hexanol; (d) 11-bromo-1-undecanol; (e) 12-bromo-1-dodecanol; (f) 2-methyl-2-propyl-1,3-propanediol; (g) 2,2-diethyl-1,3-propanediol; (h) (2-(hydroxymethyl)-1,3-propanediol; (i) 2,2,4-trimethyl-1,3-pentanediol; (j) 2-butyne-1,4-diol; (k) (xc2x1)-3,6-dimethyl-4-octyne-3,6-diol; (l) 3,6-dithia-1,8-octanediol; and (m) 2,4,7,9-tetramethyl-5-decyne-4,7-diol alkyl alcohol; an ink composition wherein the alcohol is an amino alcohol selected from the group consisting of (1) 2-(2-aminoethoxy)ethanol; (2) 2-(2-amino ethylamino) ethanol; (3) amino-1-propanol; (4) amino-1-butanol; (5) 2-amino-3-methyl-1-butanol; (6) DL-2-amino-1-hexanol; and (7) (S)-(xe2x88x92)-N-(tert-butoxycarbonyl) leucinol; an ink composition wherein the alcohol is an aromatic alcohol; an ink composition wherein the alcohol is (1) alkyl benzyl alcohol where the number of carbon atoms in the alkyl group vary from about 0 to about 8; (2) alkoxy and aryloxy benzyl alcohols where the number of carbons in the alkoxy groups vary from about 1 to 4; (3) alkyl alkyl benzyl alcohols where the number of carbons in the alkyl varies from about 1 to about 4; (4) 2-amino-3-methyl benzyl alcohol; (5) alkoxy alkoxy benzyl alcohols where the number of carbon atoms in the alkoxy group varies from about 1 to about 4; (6) 2-hydroxy-3-methoxy benzyl alcohol; (7) 3,4,5-trimethoxy benzyl alcohol; (8) phenylpropanol; (9) 3-(4-hydroxy phenyl)-1-propanol; (10) (S)-(xe2x88x92)-1-phenyl-1-butanol; (11) 2-amino-1-phenyl ethanol; (12) 3,4-dimethoxy phenethyl alcohol; (13) 2-phenyl-1,2-propane diol; (14) 3-phenoxy-1,2-propane diol; (18) phenethylalcohol, and (19) a benzyl alcohol; an ink composition wherein the lightfastness component is selected from the group consisting of (1) 1,1-(1,2-ethane diyl) bis(3,3,5,5-tetramethyl piperazinone); (2) 6-ethoxy-1,2-dihydro-2,2,4-trimethyl quinoline; (3) 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate; (4) 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)succinimide; and (5) 1,2,2,6,6-pentamethyl-4-piperidinyl/xcex2,xcex2,xcex2xe2x80x2,xcex2xe2x80x2,-tetra methyl-3,9-(2,4,8,10-tetraoxospiro(5,5)undecane)diethyl-1,2,3,4-butane tetracarboxylate; an ink composition wherein the lightfastness antioxidant compound is selected from the group consisting of (1) antimony dialkyl phosphorodithioate; (2) molybdenum oxysulfide dithio carbamate; (3) nickel-bis(o-ethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate; and (4) tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate; a printing process which comprises incorporating into an acoustic ink jet printer the invention inks, and causing droplets of the ink to be ejected in imagewise pattern onto a substrate; a process wherein there are generated developed images with crease values of from about 8 to about 15, haze values of from about 10 to about 18, gloss values of from about 85 to about 90, and which ink possesses an acoustic-loss value of from about 10 to about 80 dB/mm, and which ink possesses a viscosity of from about 1 centipoise to about 10 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C.; a process which comprises providing an acoustic ink printer having a pool of the invention inks and causing droplets of the ink to be ejected in imagewise pattern onto a substrate; a process wherein there are generated images with crease values of from about 8 to about 14, haze values of from about 10 to about 18, gloss values of from about 80 to about 95, and which ink possesses an acoustic-loss value of from about 10 to about 80 dB/mm, and which ink possesses a viscosity of from about 1 centipoise to about 10 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C.; an ink composition wherein the colorant is selected in an amount of from about 0.1 to about 20 percent by weight; an ink composition wherein the colorant is a pigment of cyan, magenta, yellow, black, or mixtures thereof; an ink composition wherein the oxazoline compound is stearyl oxazoline or distearyl oxazoline; an ink composition with a viscosity of from about 1 centipoise to about 10 centipoise, and which ink generates developed images with crease values of from about 8 to about 15, haze values of from about 10 to about 18, and gloss values of from about 85 to about 90; a composition comprised of (1) an oxazoline compound; (2) a carbamate; (3) an optional alcohol compound; (4) a lightfastness compound; (5) an antioxidant, and (6) a colorant; a composition wherein the oxazoline is a solid with a melting point of from about 60xc2x0 C. to about 120xc2x0 C. and an acoustic-loss value of from about 25 to about 80 dB/mm, and the carbamate compound possesses a melting point of from about 25xc2x0 C. to about 100xc2x0 C. and an acoustic-loss value of from about 5 to about 40 dB/mm; an ink which possesses an acoustic-loss value of from about 10 to about 80 dB/mm, and which ink possesses a viscosity of from about 1 centipoise to about 10 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C.; an ink which is substantially free of water; an ink which is free of water; an ink which is substantially water free; an ink which contains no water; inks comprised of an alkylated oxazoline such as 5-(hydroxymethyl)-5xe2x80x2(methoxy stearate)oxazoline and 2-stearyl-5-(hydroxymethyl)-5xe2x80x2(methoxy stearate)oxazoline of the formula 
and with, for example, an acoustic-loss value of from about 5 to about 40 dB/mm and a melting point of, for example about 60xc2x0 C. to about 120xc2x0 C. or with a low acoustic loss value of below, or equal to about 60 dB/mm, and preferably in the range of between about 5 to about 40 dB/mm; (2) a crease improving carbamate or thiourea additive with a melting point of lower than about 100xc2x0 C., and preferably between about 60xc2x0 C. to about 100xc2x0 C., and with a low acoustic loss value, and which acoustic loss is, for example, below about 100 dB/mm, and preferably in the range of between about 25 to about 80 dB/mm; (3) gloss improving alcohol compound; (4) a UV absorber; (5) an antioxidant; and (6) a colorant and wherein the colorant is present in various suitable amounts; an ink composition comprised of (1) a simple long chain carbamate compound or blends of long chain carbamates with a different number of carbon atoms in the side chain, for example a blend of a long chain carbamate with 16 carbon atoms in the side chain and another with 18 carbon atoms in the side chain each with a melting point of from about 25xc2x0 C. to about 100xc2x0 C.; (2) a plasticizer compound; (3) a clarifier compound; (4) a lightfastness component; (5) a lightfastness antioxidant; and (6) a colorant; an ink composition containing a solid carbamate compound possesses an acoustic-loss value of from about 5 to about 40 dB/mm; an ink composition wherein the long chain carbamate compound is present in an amount of from about 15 to about 85 percent by weight, the plasticizer is present in an amount of from about 30 to about 4 percent by weight, the clarifier is present in an amount of from about 22 to about 3 percent by weight, the lightfastness component is present in an amount of from about 5 to about 1 percent by weight, the antioxidant is present in an amount of from about 5 to about 1 percent by weight, and the colorant is present in an amount of from about 10 to about 1 percent by weight, and wherein the total amount of the ink components is about 100 percent; an ink composition wherein the plasticizer is selected from a series of Uniplex compounds (available from Unitex Chemical Corporation); an ink composition wherein the clarifier is selected from a series of Uni-Rez compounds (available from Union Camp Corporation); an ink composition wherein the lightfastness component is selected from the group consisting of (1) 1,1-(1,2-ethane diyl) bis(3,3,5,5-tetramethyl piperazinone); (2) 6-ethoxy-1,2-dihydro-2,2,4-trimethyl quinoline; (3) 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate; (4) 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)succinimide; and (5) 1,2,2,6,6-pentamethyl-4-piperidinyl/xcex2,xcex2,xcex2xe2x80x2,xcex2xe2x80x2,-tetra methyl-3,9-(2,4,8,10-tetraoxospiro(5,5)undecane) diethyl]-1,2,3,4-butane tetracarboxylate, and the like; an ink composition wherein the lightfastness antioxidant compound is selected from the group consisting of (1) antimony dialkyl phosphorodithioate; (2) molybdenum oxysulfide dithio carbamate; (3) nickel-bis(o-ethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate; and (4) tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, and the like; a process wherein there are generated developed images with crease values of from about 8 to about 16, haze values of from about 10 to about 19, gloss values of from about 85 to about 95, and which ink possesses an acoustic-loss value of from about 10 to about 80 dB/mm, and which ink possesses a viscosity of from about 1 centipoise to about 10 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C.; a process which comprises providing an acoustic ink printer having a pool of the invention inks and causing droplets of the ink to be ejected in imagewise pattern onto a substrate, such as paper; a process wherein there are generated images with crease values of from about 8 to about 14, haze values of from about 10 to about 18, gloss values of from about 80 to about 95, and which ink possesses an acoustic-loss value of from about 10 to about 80 dB/mm, and which ink possesses a viscosity of from about 1 centipoise to about 10 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C.; an ink composition wherein the colorant is selected in an amount of from about 2 to about 12 percent by weight; an ink composition wherein the colorant is a pigment of cyan, magenta, yellow, black, or mixtures thereof; an ink composition wherein the long chain carbamate has side chains with about 8 to about 20 carbon atoms; an ink composition containing blends of long chain carbamates with a different number of carbon atoms in the side chain, for example a blend of a long chain carbamate with 16 carbon atoms in the side chain and another with 18 carbon atoms in the side chain; an ink composition with a viscosity of from about 1 centipoise to about 15 centipoise, and which ink generates developed images with crease values of from about 8 to about 15, haze values of from about 10 to about 18, and gloss values of from about 85 to about 90; a composition comprised of (1) a long chain carbamate compound or blends of long chain carbamate compounds; (2) a plasticizer; (3) a clarifier; (4) a lightfastness compound; (5) an antioxidant, and (6) a colorant; a composition wherein the long chain carbamate is a solid with a melting point of from about 60xc2x0 C. to about 120xc2x0 C. and an acoustic-loss value of from about 5 to about 40 dB/mm; an ink which possesses an acoustic-loss value of from about 10 to about 80 dB/mm, and which ink possesses a viscosity of from about 1 centipoise to about 10 centipoise at a temperature of from about 125xc2x0 C. to about 165xc2x0 C.
The long chain carbamate is in embodiments a compound with, for example, a melting point of from about 60xc2x0 C. to about 120xc2x0 C., and more specifically, from about 75xc2x0 C. to about 100xc2x0 C., and is present, for example, in an amount of from about 1 to about 98 percent by weight, the plasticizer, clarifier, and mixtures thereof with, for example, an acoustic-loss value of from about 5 to about 40 dB/mm is present in the ink composition in an amount of, for example, from about 39 to about 0.5 percent by weight, the lightfastness component, such as a UV absorber is present, for example, in an amount of from about 5 to about 0.25 percent by weight, the antioxidant is, for example, present in an amount of from about 5 to about 0.25 percent by weight, and the colorant is, for example, present in an amount of from about 20 to about 0.5 percent by weight, and wherein the total of all ink components is about 100 percent. In embodiments the solid long chain carbamate compound with, for example, an acoustic-loss value of from about 5 to about 40 dB/mm is present in an amount of from about 15 to about 90 percent by weight, the crease improving plasticizer compound having a melting point of, for example, less than about 100xc2x0 C. is present in an amount of from about 35 to about 4 percent by weight, the clarifier compound with an acoustic-loss value of, for example, from about 5 to about 40 dB/mm is present in the ink composition in an amount of, for example, from about 25 to about 3 percent by weight, the lightfastness UV absorber is present in an amount of from about 5 to about 1 percent by weight, the antioxidant is present in an amount of from about 5 to about 1 percent by weight, and the colorant is present in an amount of from about 15 to about 1 percent by weight.
The oxazoline is preferably a compound with, for example, a melting point of from about 60xc2x0 C. to about 120xc2x0 C., and preferably from about 75xc2x0 C. to 100xc2x0 C., and is present, for example, in an amount of from about 1 to about 98 percent by weight, the carbamate, thiourea, or mixtures thereof with, for example, an acoustic-loss value of from about 5 to about 40 dB/mm is present in the ink composition in an amount of, for example, from about 39 to about 0.5 percent by weight, the alcohol compound with, for example, an acoustic-loss value of from about 5 to about 40 dB/mm is present in the ink composition in an amount of, for example, from about 30 to about 0.5 percent by weight, the lightfastness component, such as a UV absorber is present, for example, in an amount of from about 5 to about 0.25 percent by weight, the antioxidant is, for example, present in an amount of from about 5 to about 0.25 percent by weight, and the colorant is, for example, present in an amount of from about 20 to about 0.5 percent by weight, and wherein the total of all ink components is about 100 percent. In preferred embodiments the solid oxazoline compound with, for example, an acoustic-loss value of from about 5 to about 40 dB/mm is present in an amount of from about 15 to about 90 percent by weight, the crease improving carbamate or thiourea compound having a melting point of, for example, less than about 100xc2x0 C. is present in an amount of from about 35 to about 4 percent by weight, the gloss improving alcohol compound with an acoustic-loss value of, for example, from about 5 to about 40 dB/mm is present in the ink composition in an amount of, for example, from about 25 to about 3 percent by weight, the lightfastness UV absorber is present in an amount of from about 5 to about 1 percent by weight, the antioxidant is present in an amount of from about 5 to about 1 percent by weight, and the colorant is present in an amount of from about 15 to about 1 percent by weight.
The ink composition contains, for example, the following range amounts of (1) a solid oxazoline compound with, for example, a melting point of from about 60xc2x0 C. to about 120xc2x0 C. and an acoustic-loss value of from about 25 to about 80 dB/mm; (2) a carbamate, compound with, for example, a melting point of from about 25xc2x0 C. to about 100xc2x0 C.; (3) an alcohol compound; (4) a lightfastness component; (5) a lightfastness antioxidant; and (6) a colorant of [1+39+30+5+5+20=100] to [98+0.5+0.5+0.25+0.25+0.5=100], and preferred range amounts of [15+35+25++5+5+15=100] to [90+4+3+1+1+1=100].
The ink composition contains, for example, the following range amounts of (1) a solid long chain carbamate compound with, for example, a melting point of from about 60xc2x0 C. to about 120xc2x0 C.; or blends of long chain carbamates with different side chain lengths; (2) a plasticizer compound with, for example, a melting point of from about 25xc2x0 C. to about 100xc2x0 C.; (3) a clarifier compound; (4) a lightfastness component; (5) a lightfastness antioxidant; and (6) a colorant of [1+39+30+5+5+20=100] to [98+0.5+0.5+0.25+0.25+0.5=100], and more specific range amounts of [15+35+25++5+5+15=100] to [90+4+3+1+1+1=100].
These composition ranges, and the others indicated herein can be established using a number of known techniques, such as a statistical design based on the analyses of the experimental data of viscosity at 150xc2x0 C., jettability at 150xc2x0 C., image quality (high optical density, low crease, high gloss), lightfast, and waterfast values of images generated with various ink compositions.
Plasticizers can be incorporated in the inks in various suitable amounts, such as from about 1 percent to about 20 percent, and preferably from about 10 percent to about 15 percent to primarily reduce the ink spherulite size, and thereby improve crease, projection efficiency and haze and which plasticizers are selected from a class of compounds such as o,p-toluene sulfonamide (UNILEX 171(trademark)), p-toluene sulfonamide (UNIPLEX 173(trademark)), dicyclohexyl phthalate (UNIPLEX 250(trademark)), dimethylisophthalate (UNIPLEX 270(trademark)), pentaerythritol tetrabenzoate (UNIPLEX 552(trademark)), mixtures thereof, and other known suitable plasticizers.
Clarifying agents can be incorporated into the inks in various suitable amounts, such as from about 1 percent to about 20 percent, and more specifically, from about 10 to about 15 percent to, for example, reduce the ink spherulite size, and thereby improve crease, projection efficiency and haze and which agents can be selected from a class of compounds such as a UNI-REZ 1500/2000(trademark) series polyamide, UNI-REZ 7000/8000(trademark) series maleic rosin resins, UNI-REZ 4000/9000(trademark) series modified phenolic rosin resins, mixtures thereof and the like. Blending of two long chain carbamates with different side chain lengths, for example, one with 17 carbon atoms and the other with 20 carbon atoms in the side chain, can also reduce the spherulite size and improves crease, projection efficiency and haze. The amount of plasticizers and clarifiers in the ink compositions can be reduced to suitable amounts or one of them eliminated altogether, and wherein the total of all ink components is about 100 percent.
The carbamate compounds, which can function as a crease agent, with, for example, a melting point of less than about 100xc2x0 C. and an acoustic-loss value of, for example, of from about 5 to about 40 dB/mm is, for example, selected from the group consisting of (1) butyl carbamate (Aldrich #B9,080-7); (2) tert-butyl carbamate (Aldrich #16,739-8); (3) tert-butyl N-(3-aminopropyl) carbamate (Aldrich #43,699-2); (4) tert-butyl N-(3-hydroxypropyl) carbamate (Aldrich #41,644-4); (5) tert-butyl-N-[benzyloxy)carbamate (Aldrich #40,769-0); (6) tert-butyl-N-hydroxycarbamate (Aldrich #22,615-7); (7) tert-butyl-N-allylcarbamate (Aldrich #42,233-9); (8) tert-butyl-N-(tert-butoxycarbonyloxy) carbamate (Aldrich #41,279-1); (9) tert-butyl-N-[2-hydroxy-2-(hydroxyphenyl)-1-methylethyl]carbamate (Aldrich #40,429-2); (10) tert-butyl-(2,4-dinitrophenoxy) carbamate (Aldrich #33,305-0); (11) benzyl carbamate (Alfa Organics #A11569); (12) benzyl N-hydroxycarbamate (Aldrich #32,327-6); (13) benzyl N-(2-hydroxyethyl)carbamate (Aldrich #40,790-9); (14) benzyl-N,N-dimethyldithiocarbamate (Aldrich #36,822-9); (15) ethyl N-methyl-N-phenylcarbamate (Aldrich #30,951-6); (16) ethyldiphenyl carbamate (Aldrich #37,291-9); (17) cyanomethyl-N,N-dimethyl dithiocarbamate (Aldrich #28,054-2); (18) 4,4xe2x80x2-methylene-bis(dibutyldithio carbamate), Vanlube 7723, Vanderbilt Corporation; (19) potassium N-hydroxy methyl-N-methyl-dithiocarbamate (Busan 40 from Buckman Laboratories Inc.); (20) sodium dimethyl dithiocarbamate; (21) disodium ethylenebis-dithio carbamate; (22) diethylammonium diethyldithio carbamate (Alfa Organics #A10458); (23) benzyl(S)-(xe2x88x92)-tetrahydro-5-oxo-3-furanyl carbamate (Aldrich #41,924-9); (24) diethyldithiocarbamic acid, ammonium salt (Aldrich #35,954-8); (25) diethyldithiocarbamic acid, diethyl ammonium salt (Aldrich #31,811-6); (26) diethyldithiocarbamic acid, sodium salt, trihydrate (Aldrich #22,868-0); (27) 4-bromo-3,5-dimethylphenyl N-methylcarbamate (Aldrich #34,694-2), and the like. Examples of specific straight chain carbamates, with in embodiments a melting point of about equal to or above 60 degrees Centigrade, and more specifically from about 65 to about 90 degrees Centigrade, include stearylcarbamoyl octanoate, stearylcarbamoyl dodecanoate, stearylcarbamoyl hexadecanoate, stearylcarbamoyl octadecanoate, and the like.
The thiourea compound, which can function as a crease agent, with, for example, a melting point of between about 25xc2x0 C. to about 100xc2x0 C. and an acoustic-loss value of, for example, from about 5 to about 40 dB/mm are selected, for example, from the group consisting of (1) 1-allyl-2-thiourea (Aldrich #10,880-41); (2) 1-allyl-3-(2-hydroxyethyl)-2-thiourea (Aldrich #A3,280-2); (3) 1-methyl-2-thiourea (Aldrich #M8, 460-7); (4) 1-methallyl-3-methyl-2-thiourea (Aldrich #19,046-2); (5) 1,3-dibutyl-2-thiourea (Aldrich #D4,959-8); (6) 1,1,3,3-tetramethyl-2-thiourea (Aldrich #11,516-9); (7) N,Nxe2x80x2-di-n-propyl thiourea (Alfa Organics #A17217); (8) 1-benzyl-3-methyl-2-thiourea (Aldrich #27,550-6), and the like.
Oxazoline examples include known suitable oxazolines, such as hydroxy alkoxy oxazolines, and more specifically, (1) 5-(hydroxymethyl)-5xe2x80x2(methoxy stearate)oxazoline; (2) 2-stearyl-5-(hydroxymethyl)-5xe2x80x2(methoxy stearate)oxazoline; and (3) mixtures thereof.
Examples of alcohols include various suitable alcohols such as
(A) cyclic alcohols such as (1) cycloalkyl alcohols where the number of carbons in the alkyl chain vary from 6 to 12 and preferably from about 8 to 10 such as cyclohexanol (Aldrich #10,589-9), cycloheptanol (Aldrich #C9,880-2), cyclododecanol (Aldrich #C9,740-7); (2) 4-tert-butyl cyclohexanol (Aldrich #B9,200-1); (3) 3-aminomethyl-3,5,5-trimethyl cyclohexanol (Aldrich #19,479-4); (4) 2,2,6,6-tetrachloro cyclohexanol (Aldrich #18,681-3); (5) cycloalkane methanol where the number of carbons in the alkane chain vary from about 5 to about 12 and preferably from about 8 to about 10 such as cyclopentane methanol (Aldrich #10,398-5), cyclohexane methanol (Aldrich #C10,580-5), cycloheptane methanol (Aldrich #13,865-7), cyclododecane methanol (Aldrich #11,224-0); (6) dicyclohexylmethanol (Aldrich #31,772-1); (7) 3-cyclohexyl-1-propanol (Aldrich #30,440-9); (8) 2-amino-3-cyclohexyl-1-propanol (Aldrich #42,161-8); (9) (S)-2-(tert-butoxycarbonylamino)-3-cyclohexyl-1-propanol (Aldrich #42,169-3); (10) cycloalkane diol where the number of carbons in the alkane chain vary from about 5 to about 9, and preferably from about 6 to about 8 such as 1,2-cyclopentanediol (Aldrich #36,144-5), 1,3-cyclohexanediol (Aldrich #C10,110-9), 1,2-cyclohexanediol (Aldrich #36,126-7; 14,171-2), 1,4-cyclohexane diol (Aldrich #C10,120-6), cyclooctanediol (Aldrich #17,903-5; 36,223-9); (11) cis-3,5-cyclohexadiene-1,2-diol (Aldrich #36,506-8); (12) xcfx81-menthane-3,8-diol (Aldrich #38,404-6;38,405-4); (13) cyclohexane dimethanol (Aldrich #12,559-8, Aldrich #18,908-1); (14) 1,3-dioxane-5,5-dimethanol (Aldrich #22,062-0); (15) 3-cyclohexene-1,1-dimethanol (Aldrich #16,215-9); (16) piperidine methanol (Aldrich #15,522-5, Aldrich #15,523-3);
(B) linear alcohols such as (1) alkyl alcohols where the number of carbons in the alkyl chain can vary from about 1 and preferably from about 6 to 22, and more preferably from about 10 to about 16, such as hexyl alcohol (Aldrich #H1330-3), heptyl alcohol (Aldrich #H280-5), octyl alcohol (Aldrich #29,324-5), nonyl alcohol (Aldrich #13,121-0), decylalcohol (Aldrich #23,976-3), undecyl alcohol (Aldrich #U 100-1), 1-dodecanol (Aldrich #12,679-9), 1-tetradecanol (Aldrich #18,538-8), 1-pentadecanol (Aldrich #41,222-8), 1-hexadecanol (Aldrich #25,874-1), 1-eicosanol (Aldrich #23,449-4), 1-docosanol (Aldrich #16,910-2); (2) alkane diols where the number of carbons in the alkane chain vary from, for example, about 1, and more specifically, from about 5 to about 14, and preferably from about 8 to about 12, such as 1,5-pentane diol (Aldrich #P770-3), 1,6-hexane diol (Aldrich #H1,180-7), 1,7-heptane diol (Aldrich #H220-1), 1,2-octane diol (Aldrich #21,370-5), 1,8-octane diol (Aldrich #O,330-3), 1,9-nonane diol (Aldrich #N2,960-0), 1,10-decane diol (Aldrich #D,120-3), 1,2-decane diol (Aldrich #26,032-0), 1,2-dodecane diol (Aldrich #21,372-1), 1,12-dodecane diol (Aldrich #D22,130-9), 1,2-tetradecane diol (Aldrich #26,029-0), 1,14-tetradecane diol (Aldrich #29,901-4); (3) 5-amino-1-pentanol (Aldrich #12,304-8); (4) nitromethane trispropanol (Aldrich #36,153-4); (5) 6-amino-1-hexanol (Aldrich #A5,645-0); (6) 11-bromo-1-undecanol (Aldrich #18,413-6); (7) 12-bromo-1-dodecanol (Aldrich #22,467-7); (8) 2-methyl-2-propyl-1,3-propane diol (Aldrich #M7,520-9); (9) 2,2-diethyl-1,3-propanediol (Aldrich #D10,000-5); (10) (2-(hydroxymethyl)-1,3-propanediol (Aldrich #39,365-7); (11) 2,2,4-trimethyl-1,3-pentanediol (Aldrich #32,722-0); (12) 2-butyne-1,4-diol (Aldrich #B10,320-9); (13) (xc2x1)-3,6-dimethyl-4-octyne-3,6-diol (Aldrich #27,840-8); (14) 3,6-dithia-1,8-octanediol (Aldrich #23,533-4); (15) 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Aldrich #27,838-6);
(C) amino alcohols such as: (1) 2-(2-aminoethoxy)ethanol (Aldrich #A5,405-9); (2) 2-(2-amino ethylamino)ethanol (Aldrich #12,758-2); (3) amino-1-propanol (Aldrich #23,886-4, 29,768-2, 19,217-1, A7,620-6; 23,984-4); (4) 2-amino-1-butanol (Aldrich #A4,380-6); (5) 4-amino-1-butanol (Aldrich #17,833-0); (6) 2-amino-3-methyl-1-butanol (Aldrich #18,483-7); (7) DL-2-amino-1-hexanol (Aldrich #23,767-1); (8) (S)-(xe2x88x92)-N-(tert-butoxycarbonyl)leucinol (Aldrich #44,119-8);
(D) aromatic alcohols such as (1) alkyl benzyl alcohols where the number of carbon atoms in the alkyl group vary from, for example, 0 to about 8, and preferably from about 4 to about 6, such as benzyl alcohol (Aldrich #10,800-6), 3-methyl benzyl alcohol (Aldrich #18,821-2), 4-methyl benzyl alcohol (Aldrich #12,780-9), 2-phenyl benzyl alcohol (Aldrich #18,882-4), 2-phenethyl benzyl alcohol (Aldrich #18,478-0); (2) alkoxy and aryloxy benzyl alcohols where the number of carbons in the alkoxy groups vary from, for example, about 1 to about 4 such as 2-methoxy benzyl alcohol (Aldrich #M1,080-8), 3-methoxybenzyl alcohol (Aldrich #M1,100-6), 4-methoxy benzyl alcohol (Aldrich #13,690-5), 2-ethoxy benzyl alcohol (Aldrich #19,066-7), 4-ethoxy benzyl alcohol (Aldrich #19,047-0), 4-butoxy benzyl alcohol (Aldrich #18,424-1), and in the aryloxy groups preferably from about 6 to about 8 carbons, such as 3-benzyloxy benzyl alcohol; (3) alkyl alkyl benzyl alcohols where the number of carbons in the alkyl varies, for example, from about 1 to about 4 such as 2,4-dimethyl benzyl alcohol (Aldrich #18,878-6), 2,5-dimethyl benzyl alcohol (Aldrich #18,932-4), 3,5-dimethyl benzyl alcohol (Aldrich #19,999-0), 3,4-dimethyl benzyl alcohol (Aldrich #18,879-4); (4) 2-amino-3-methyl benzyl alcohol (Aldrich #33,419-7); (5) alkoxy alkoxy benzyl alcohols where the number of carbon atoms in the alkoxy group varies, for example, from about 1 to about 4 such as 2,4-dimethoxy benzyl alcohol (Aldrich #15,963-8), 3,5-dimethoxy benzyl alcohol (Aldrich #19,165-5), 2,3-dimethoxy benzyl alcohol (Aldrich #12,631-4), 3-ethoxy-4-methoxy benzyl alcohol (Aldrich #30,790-4), 4-ethoxy-3-methoxy benzyl alcohol (Aldrich #18,914-6); (6) 2-hydroxy-3-methoxy benzyl alcohol (Aldrich #30,596-0); (7) 3,4,5-trimethoxy benzyl alcohol (Aldrich #T7,000-9);
(E) phenyl alcohol derivatives such as (1) phenylpropanol (Aldrich #P3,080-2, Aldrich #14,085-6); (2) 3-(4-hydroxyphenyl)-1-propanol (Aldrich #19,741-6); (3) (S)-(xe2x88x92)-1-phenyl-1-butanol (Aldrich #31,731-4); (4) 2-amino-1-phenylethanol (Aldrich #A7,240-5); (5) 3,4-dimethoxy phenethyl alcohol (Aldrich #19,765-3); (6) 2-phenyl-1,2-propane diol (Aldrich #21,376-4); (7) 3-phenoxy-1,2-propane diol (Aldrich #10,819-7); (8) 3-methoxy catechol (Aldrich #M1,320-3); (9) benzhydrol (Aldrich #B,485-4); (10) methyl benzhydrol, (Aldrich #18,995-2; Aldrich #18,996-0); (11) phenethyl alcohol (Aldrich #P1,362-2); (12) 4-methoxy phenethyl alcohol (Aldrich #15,418-0); (13) 2-hydroxy phenethyl alcohol (Aldrich #18,824-7, Aldrich #19,902-8); (14) 2-amino phenethylalcohol (Aldrich #19,260-0); and the like.
Lightfastness components, that primarily protect the developed images from UV degradation are known and include (1) N-p-ethoxycarbonylphenyl)-Nxe2x80x2-ethyl-Nxe2x80x2-phenylformadine, Givaudan Corporation; (2) 1,1-(1,2-ethane-diyl) bis(3,3,5,5-tetramethyl piperazinone), Goodrich Chemicals; (3) 2,2,4-trimethyl-1,2-hydroquinoline, Mobay Corporation; (4) 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, Monsanto-Chemicals; (5) 2,4,6-tris-(N-1,4-dimethylpentyl-4-phenylenediamino)-1,3,5-triazine, Uniroyal Corporation; (6) 2-(4-benzoyl-3-hydroxy phenoxy)ethylacrylate; (7) 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl) succinimide; (8) 2-dodecyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl) succinimide; (9) N-(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecyl succinimide, all four available from Aldrich Chemicals; (10) 2,2,6,6-tetramethyl-4-piperidinyl/xcex2,xcex2,xcex2xe2x80x2,xcex2xe2x80x2-tetramethyl-3,9-(2,4,8,10-tetraoxospiro(5,5)-undecane)diethyl]-1,2,3,4-butane tetracarboxylate; (11) [1,2,2,6,6-pentamethyl-4-piperidinyl/xcex2,xcex2,xcex2xe2x80x2,xcex2xe2x80x2-tetramethyl-3,9-(2,4,8,10-tetraoxo-spiro-(5,5)undecane)diethyl]-1,2,3,4-butanetetra carboxylate; (12) [2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, all three available from Fairmont Corporation; (13) nickel dibutyl dithio carbamate, available as UV-Chek AM-105 from Ferro Corporation.
Lightfastness antioxidants that primarily protect the developed images from oxidation include (1) antimony dialkyl phosphorodithioate; (2) molybdenum oxysulfide dithio carbamate, both available from Vanderbilt Corporation; (3) (nickel-bis(o-ethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, Ciba Geigy Corporation; (4) tetra sodium-N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, American Cyanamid Corporation, and the like.
Suitable colorants, present in an effective amount generally of from about 1 to about 25, and, for example from about 2 to about 12 weight percent, include pigments and dyes, with solvent dyes being preferred. Any dye or pigment may be chosen, provided that it is capable of being dispersed or dissolved in the vehicle and is compatible with the other ink components. Colorants include pigments, dyes, mixtures thereof, mixtures of dyes, mixtures of pigments, and the like.
Examples of suitable pigments include Violet Toner VT-8015 (Paul Uhlich); Paliogen Violet 5100 (BASF); Paliogen Violet 5890 (BASF); Permanent Violet VT 2645 (Paul Uhlich); Heliogen Green L8730 (BASF); Argyle Green XP-111-S (Paul Uhlich); Brilliant Green Toner GR 0991 (Paul Uhlich); Lithol Scarlet D3700 (BASF); Toluidine Red (Aldrich); Scarlet for Thermoplast NSD PS PA (Ugine Kuhlmann of Canada); E.D. Toluidine Red (Aldrich); Lithol Rubine Toner (Paul Uhlich); Lithol Scarlet 4440 (BASF); Bon Red C (Dominion Color Company); Royal Brilliant Red RD-8192 (Paul Uhlich); Oracet Pink RF (Ciba-Geigy); Paliogen Red 3871 K (BASF); Paliogen Red 3340 (BASF); Lithol Fast Scarlet L4300 (BASF); Heliogen Blue L6900, L7020 (BASF); Heliogen Blue K6902, K6910 (BASF); Heliogen Blue D6840, D7080 (BASF); Sudan Blue OS (BASF); Neopen Blue FF4012 (BASF); PV Fast Blue B2G01 (American Hoechst); Irgalite Blue BCA (Ciba-Geigy); Paliogen Blue 6470 (BASF); Sudan III (Red Orange), (Matheson, Colemen Bell); Sudan II (Orange), (Matheson, Colemen Bell); Sudan Orange G (Aldrich); Sudan Orange 220 (BASF); Paliogen Orange 3040 (BASF); Ortho Orange OR 2673 (Paul Uhlich); Paliogen Yellow 152,1560 (BASF); Lithol Fast Yellow 0991K (BASF); Paliotol Yellow 1840 (BASF); Novoperm Yellow FGL (Hoechst); Permanent Yellow YE 0305 (Paul Uhlich); Lumogen Yellow D0790 (BASF); Suco-Yellow L1250 (BASF); Suco-Yellow D1355 (BASF); Suco Fast Yellow D1355, D1351 (BASF); Hostaperm Pink E (American Hoechst); Fanal Pink D4830 (BASF); Cinquasia Magenta (Du Pont); Paliogen Black L0084 (BASF); Pigment Black K801 (BASF); and carbon blacks, such as REGAL 330(copyright) (Cabot), Carbon Black 5250, Carbon Black 5750 (Columbian Chemical Company).
Dye examples include Pontamine; Food Black 2; Carodirect Turquoise FBL Supra Conc. (Direct Blue 199), available from Carolina Color and Chemical; Special Fast Turquoise 8 GL Liquid (Direct Blue 86), available from Mobay Chemical; Intrabond Liquid Turquoise GLL (Direct Blue 86), available from Crompton and Knowles; Cibracron Brilliant Red 38-A (Reactive Red 4), available from Aldrich Chemical; Drimarene Brilliant Red X-2B (Reactive Red 56), available from Pylam, Inc.; Levafix Brilliant Red E-4B, available from Mobay Chemical; Levafix Brilliant Red E6- BA, available from Mobay Chemical; Procion Red H8B (Reactive Red 31), available from ICI America; Pylam Certified DandC Red #28 (Acid Red 92), available from Pylam; Direct Brill Pink B Ground Crude, available from Crompton and Knowles; Cartasol Yellow GTF Presscake, available from Sandoz, Inc.; Tartrazine Extra Conc. (FDandC Yellow #5, Acid Yellow 23), available from Sandoz, Inc.; Carodirect Yellow RL (Direct Yellow 86), available from Carolina Color and Chemical; Cartasol Yellow GTF Liquid Special 110, available from Sandoz, Inc.; DandC Yellow #10 (Acid Yellow 3), available from Tricon; Yellow Shade 16948, available from Tricon; Basacid Black X 34, available from BASF; Carta Black 2GT, available from Sandoz, Inc.; and the like. Particularly preferred are solvent dyes, and within the class of solvent dyes, spirit soluble dyes are preferred because of their compatibility with the vehicles and dye leveling compounds of the present application. Examples of suitable spirit solvent dyes include Neozapon Red 492 (BASF); Orasol Red G (Ciba-Geigy); Direct Brilliant Pink B (Crompton-Knolls); Aizen Spilon Red C-BH (Hodogaya Chemical Company); Kayanol Red 3BL (Nippon Kayaku Company); Levanol Brilliant Red 3BW (Mobay Chemical Company); Levaderm Lemon Yellow (Mobay Chemical Company); Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (Hodogaya Chemical Company); Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (Sandoz); Pergasol Yellow CGP (Ciba-Geigy); Orasol Black RLP (Ciba-Geigy); Savinyl Black RLS (Sandoz); Dermacarbon 2GT (Sandoz); Pyrazol Black BG (ICI); Morfast Black Conc. A (Morton-Thiokol); Diaazol Black RN Quad (ICI); Orasol Blue GN (Ciba-Geigy); Savinyl Blue GLS (Sandoz); Luxol Blue MBSN (Morton-Thiokol); Sevron Blue 5GMF (ICI); Basacid Blue 750 (BASF), and the like. Neozapon Black X51 (C.I. Solvent Black; C.I. #12195) (BASF); Sudan Blue 670 (C.I. #61554) (BASF); Sudan Yellow 146 (C.I. #12700) (BASF); Sudan Red 462 (C.I. #26050) (BASF) are preferred.
The inks of the present invention can be prepared by any suitable method, such as simple mixing of the components. More specifically, a colored phase-change ink composition can be prepared by mixing 70 percent by weight of the compound 2-stearyl-5-(hydroxymethyl)-5xe2x80x2(methoxy stearate) oxazoline having an acoustic-loss value of about 40 dB/mm and a melting point of between 60xc2x0 C. to 120xc2x0 C.; 10 percent by weight of a crease improving compound derived from carbamates, or thioureas and having a melting point of between about 50xc2x0 C. to about 95xc2x0 C.; 5 percent by weight of a gloss improving alcohol compound; 5 percent by weight of a lightfast UV absorber; 5 percent by weight of lightfast antioxidant; and 5 percent by weight of a colorant. The mixture resulting can then be heated to a temperature of about 120xc2x0 C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently was cooled to 25xc2x0 C. More specifically, a colored phase-change ink composition can be prepared in embodiments by mixing about 70 percent by weight of the long chain carbamate compound or blends of two long chain carbamates thereof having an acoustic-loss value of about 40 dB/mm and a melting point of between about 60xc2x0 C. to about 120xc2x0 C.; about 10 percent by weight of a crease improving plasticizer compound such as o,p-toluene sulfonamide (UNILEX 171(trademark)), p-toluene sulfonamide (UNIPLEX 173(trademark)), dicyclohexyl phthalate (UNIPLEX 250(trademark)), dimethylisophthalate (UNIPLEX 270(trademark)), pentaerythritol tetrabenzoate (UNIPLEX 552(trademark)), or mixtures thereof with a melting point of between about 25xc2x0 C. to about 100xc2x0 C.; about 10 to about 20 percent by weight of a clarifying agent such as a UNI-REZ 1500/2000(trademark) series polyamide, UNI-REZ 7000/8000(trademark) series maleic rosin resins, UNI-REZ 4000/9000(trademark) series modified phenolic rosin resins, or mixtures there of; 5 percent by weight of a lightfast UV absorber; about 5 percent by weight of lightfast antioxidant; and about 5 percent by weight of a colorant. The mixture resulting can then be heated to a temperature of about 120xc2x0 C. and stirred for a period of about 60 minutes until it formed a homogeneous solution, and subsequently was cooled to 25xc2x0 C.
The inks of the present invention are particularly suitable for use in acoustic ink jet printing processes. In acoustic ink jet printing, reference a number of the copending applications and patents recited here, the disclosures of which have been totally incorporated herein by reference, an acoustic beam exerts a radiation pressure against objects upon which it impinges. Thus, when an acoustic beam impinges on a free surface of the ink of a pool of liquid from beneath, the radiation pressure which it exerts against the surface of the pool may reach a sufficiently high level to release individual droplets of liquid from the pool, despite the restraining force of surface tension. Focusing the beam on or near the surface of the pool intensifies the radiation pressure it exerts for a given amount of input power, reference, for example, the copending applications, and the appropriate patents recited herein, and IBM Technical Disclosure Bulletin, Vol. 16, No. 4, September 1973, pages 1168 to 1170, the disclosure of which is totally incorporated herein by reference. Acoustic ink printers typically comprise one or more acoustic radiators for illuminating the free surface of a pool of liquid ink with respective acoustic beams. Each of these beams usually is brought to focus at or near the surface of the reservoir (i.e., the liquid/air interface). Furthermore, printing conventionally is performed by independently modulating the excitation of the acoustic radiators in accordance with the input data samples for the image that is to be printed. This modulation enables the radiation pressure, which each of the beams exerts against the free ink surface, to make brief, controlled excursions to a sufficiently high pressure level for overcoming the restraining force of surface tension. That, in turn, causes individual droplets of ink to be ejected from the free ink surface on demand at an adequate velocity to cause them to deposit in an image configuration on a nearby recording medium. The acoustic beam may be intensity modulated or focused/defocused to control the ejection timing or an external source may be used to extract droplets from the acoustically excited liquid on the surface of the pool on demand. Regardless of the timing mechanism employed, the size of the ejected droplets is determined by the waist diameter of the focused acoustic beam. Acoustic ink printing is attractive because it does not require the nozzles or the small ejection orifices which have caused many of the reliability and pixel placement accuracy problems that conventional drop on demand and continuous stream ink jet printers have suffered.
Pixel placement accuracy problems that conventional drop on demand and continuous stream ink jet printers has suffered. The size of the ejection orifice is a critical design parameter of an ink jet because it determines the size of the droplets of ink that the jet ejects. As a result, the size of the ejection orifice cannot be increased without sacrificing resolution. Acoustic printing has increased intrinsic reliability since usually there are no nozzles to clog. Furthermore, small ejection orifices are avoided, so acoustic printing can be performed with a greater variety of inks than conventional ink jet printing, including inks having higher viscosities and inks containing pigments and other particulate components. Acoustic ink printers embodying printheads comprising acoustically illuminated spherical focusing lenses can print precisely positioned pixels (picture elements) at resolutions which are sufficient for high quality printing of relatively complex images. It has also been determined that the size of the individual pixels printed by such a printer can be varied over a significant range during operation, thereby accommodating, for example, the printing of variably shaded images. Furthermore, the known droplet ejector technology can be adapted to a variety of printhead configurations, including (1) single ejector embodiments for raster scan printing; (2) matrix configured ejector arrays for matrix printing; and (3) several different types of pagewidth ejector arrays, ranging from (i) single row, sparse arrays for hybrid forms of parallel/serial printing to (ii) multiple row staggered arrays with individual ejectors for each of the pixel positions or addresses within a pagewidth image field (i.e., single ejector/pixel/line) for ordinary line printing. Inks suitable for acoustic ink jet printing typically are liquid at ambient temperatures (i.e., about 25xc2x0 C.), however in other embodiments, the ink is in a solid state at ambient temperatures and provision is made for liquefying the ink by heating or any other suitable method prior to introduction of the ink into the printhead. Images of two or more colors can be generated by several methods, including by processes wherein a single printhead launches acoustic waves into pools of different colored inks. Further information regarding acoustic ink jet printing apparatus and processes is disclosed in, for example, U.S. Pat. Nos. 4,308,547, 4,697,195, 5,028,937, 5,041,849, 4,751,529, 4,751,530, 4,751,534, 4,801,953, and 4,797,693, the disclosures of each of which are totally incorporated herein by reference. The use of focused acoustic beams to eject droplets of controlled diameter and velocity from a free-liquid surface is also described in J. Appl. Phys., vol. 65, no. 9 (May 1, 1989) and references therein, the disclosure of which is totally incorporated herein by reference.
The oxazoline, carbamate, alcohols, the lightfastness compound, such as a UV absorber, and the antioxidant are preferably crystalline or semicrystalline in the solid state. A material is considered crystalline if it is primarily comprised of crystals having regular arrangement of its atoms in the space lattice. When this arrangement of atoms in the space lattice is irregular, the material is considered as amorphous. The in between state with part of the structure crystalline and another part as amorphous is called semicrystalline. When solidified on a substrate such as paper or transparency, the invention phase change ink materials crystallize in spherulitic morphology, and wherein the size of the spherulites is preferably, for example, from about 0.1 to about 10 microns, and most preferably between about 1 and about 4 microns, for optimum projection efficiency. The spherulite size can be measured by an optical microscope with cross polarized light or by the low angle solid state light scattering method (R. S. Stein and M. B. Rhodes, J. Appl. Phys., 31, 1873 (1960)). A monochromatic, vertically polarized light is passed through the sample. The scattered light is analyzed with another nicol prism, with its optic axis horizontal, known as the Hv scattering method. The spherulite size is measured from the location of the maximum intensity in the four-leaf clover scattering pattern. Large spherulites, of size greater than about 10 microns may result in brittle prints. The size of the spherulites can be controlled by, for example formulating ternary blends of oxazoline, carbamates and alcohols. When solidified, the oxazoline, carbamate and alcohol can form a disperse phase of small spherulitic crystalline domains in the matrix of each other. This morphology of reduced spherulitic size of from, for example preferably between about 0.5 to about 1 micrometer measured with an optical microscope improves the projection efficiency, and increases the crease resistance. Inks with a spherulite size of between about 0.5 to about 1 micrometer are ideal as these scatter a minimum amount of light thereby improving projection efficiency when printed on transparencies. The resistance to creasing is also increased with reduced spherulite size because primarily of excellent intra molecular bonding between the ink molecules.
The long chain simple carbamates, the plasticizer, clarifier, lightfastness compound, such as a UV absorber, and the antioxidant are preferably crystalline or semicrystalline in the solid state. A material is considered crystalline if it is primarily comprised of crystals having regular arrangement of its atoms in the space lattice. When this arrangement of atoms in the space lattice is irregular, the material is considered as amorphous. The in between state with part of the structure crystalline and another part as amorphous is called semicrystalline. When solidified on a substrate such as paper or transparency, the invention phase change ink materials crystallize in spherulitic morphology, and wherein the size of the spherulites is preferably, for example, from about 0.1 to about 10 microns, and most preferably between about 0.1 to about 4 microns, for optimum projection efficiency. The spherulite size can be measured by an optical microscope with cross polarized light or by the low angle solid state light scattering method (R. S. Stein and M. B. Rhodes, J. Appl. Phys., 31, 1873 (1960)). A monochromatic, vertically polarized light is passed through the sample. The scattered light is analyzed with another nicol prism, with its optic axis horizontal, known as the Hv scattering method. The spherulite size is measured from the location of the maximum intensity in the four-leaf clover scattering pattern. Large spherulites, of size greater than about 10 microns may result in brittle prints. The size of the spherulites can be controlled by, for example formulating binary or ternary blends of two or more long chain carbamates with different side chain lengths, for example, one with 16 carbon atoms and the other with 18 carbon atoms in the side chain, thereby also improving the crease, projection efficiency and haze. In this case, the amount of plasticizers and clarifiers in the compositions can be reduced to suitable amounts or one of them eliminated altogether.
When solidified, the mixtures of long chain carbamates, plasticizers and clarifiers can form a dispersed phase of small spherulitic crystalline domains in the matrix of each other. This morphology of reduced spherulitic size of from, for example, between about 0.1 to about 1 micrometer measured with an optical microscope or light scattering can improve the projection efficiency, and increase the crease resistance. Inks with a spherulite size of between about 0.1 to about 1 micrometer can scatter a minimum amount of light thereby improving projection efficiency when printed on transparencies. The resistance to creasing can also be increased with reduced spherulite size.
Acoustic-loss measurements were measured as follows: samples of various liquid vehicles, such as the oxazoline, and carbamate were placed between the two transducers, with the temperature set at 150xc2x0 C. The samples were allowed equilibrate at 150xc2x0 C. for five minutes. The two transducers were brought together to maximize the acoustic signal. The amplitude and the position of the signals were recorded. The two transducers were separated by a distance varying from 25.4 microns to 125.4 microns recording each time the amplitude and the position of the signal. Each measurement was performed three times and three samples of the same material were measured. The attenuation dB/mm was then calculated by ratioing the amplitude values obtained at different separation distances.
The optical density values of, for example, black (Neozapon Black X51, C.I. #12195) between 2.1 to 2.3, cyan (Sudan Blue 670, C.I. #61554) between 1.80 to 1.85, Magenta Sudan Red 462 (C.I. #26050), between 1.90 to 1.95 and yellow (Sudan Yellow 146, C.I. #12700) between 1.37 to 1.45, recited herein were obtained on a Pacific Spectrograph Color System. This system consists of two major components, an optical sensor and a data terminal. The optical sensor employs a 6-inch integrating sphere to provide diffuse illumination and 8 degrees viewing. This sensor can be used to measure both transmission and reflectance samples. When reflectance samples are measured, a specular component may be included. A high resolution, full dispersion, grating monochromator was used to scan the spectrum from 380 to 720 nanometers. The data terminal features a 12 inch CRT display, numerical keyboard for selection of operating parameters and the entry of tristimulus values, and an alphanumeric keyboard for entry of product standard information.
The lightfast values were measured in the Mark V Lightfast Tester obtained from Microscal Company, London, England; and the waterfast values of the ink jet images were obtained with an optical density data recorded before and after washing with water at 25xc2x0 C. for five minutes.
The viscosity was measured at 150xc2x0 C. with a Stress Rheometer from Cari-Med model CSL 100. All experiments were performed at a shear rate of 1250 sxe2x88x921.
The average width of the creased image due to pressure was obtained on colored and black solid area images printed on paper by (a) folding inwards the printed area of the image; (b) passing on the folded image a standard TEFLON coated copper roll 2 inches in width, 3 inches in outer diameter, 2.25 inches in inner diameter and weighing 860 grams; (c) unfolding the paper and wiping the loose toner from the creased imaged surface with a cotton swab; (d) measuring the average width of the toner free creased area with an image analyzer.
The haze values of the images between, for example, about 10 to about 30, and preferably between about 10 to about 20, were measured on images printed on uncoated polyester, such as MYLAR(copyright), with a Haze meter XL-211, HAZEGARD(copyright) System obtained from Pacific Scientific Company.
The following specific Examples are provided. These examples are intended to be illustrative, and the invention is not limited to the materials, conditions, or process parameters set forth. All parts and percentages are by weight unless otherwise indicated. The alkylated [2-stearyl-5-(hydroxymethyl)-5xe2x80x2(methoxy stearate)oxazoline]oxazolines can be prepared as follows: To a one liter Parr reactor equipped with a bottom drain valve, double turbine agitator, and distillation receiver with a cold water condenser were charged 568 grams of steric acid, 120 grams of tris(hydroxymethyl) amino methane and 0.6 gram of butyltin hydroxide oxide as the catalyst. The reactor, exposed to the atmosphere, was slowly heated to 100xc2x0 C., and stirring was commenced. The reactor was carefully heated to a final temperature of 180xc2x0 C. and kept constant for 30 minutes. As the condensation reaction to yield the product distearyl-oxazoline progressed, water, the byproduct was distilled and collected. House vacuum was then applied to remove the final residual traces of water. The reaction was then cooled to 75xc2x0 C., and discharged as pale yellow liquid, which solidified to an off-white solid upon further cooling. The melting point of the solid was between 61xc2x0 C. to 62xc2x0 C. 1H NMR and IR spectroscopy confirmed the structure of the material.